Modified polyhydric alcohol-polybasic acid resins and compositions containing them



Patented ov. 5, 1935 re s MODIFIED POLYHYDRIC ALCOHOL-POLY- BASIC ACID BESINS AND COMPOSITIONS CONTAINING THEM Ben E. Sorenson, Wilmington, DeL, assignor to E. I. du Pont de Nemours & Company, Wilmington, DeL, a corporation of Delaware No Drawing. Application February 11,1929, Serial No. 339,265

20 Claims. (01. 250-8) This invention relates to the art of polyhydric 225 C. For the composition of Example 1 this alcohol-polybasic acid resins and, more particurequires about '4 hours. The resinification is larly, to modified polyhydric alcohol-polybasic then finished asinExample 1.

' acid resins and compositions containing them. E z 2 I have discovered that polyhyd-ric alcoholv "camp 6 1 polybasic acid resins, which are the reaction 17.9 parts by weight of glycerol, 58.7 parts by products of polyhydric alcohols and polybasic weight of phthalic anhydride and 25.8 parts by acids, with or without other ingredients, can be weight of the monoethyl ether of diethylene glyrendered more flexible and resilient than has col are heated together in a suitable covered con- 10 heretofore been possible by esterifying hydro tainer. The temperature is gradually raised to 10 others with the other. ingredients. 225 C. in 3-4 hours with the container covered It is therefore an object of this invention to to prevent volatilization of the ether as much provid new and useful m difi d p lyhydric 2.1- as possible. When the boiling point of the recohol-polybasic acid resins. action mixture has been raised due to esterifica- It is another object of this inve] on toprovide tion so that the loss of ether is negligible, the 15 a process of producing more flexib e and resilient lid is removed and the heating at 225 C. is consynthetic resins. tinued until the desired viscosity is obtained.

It is also an object 01' this invention to provide The time required to attain a consistency such new d imPI'OVBd mating compositions t that the hot resin begins to string when allowed in y m fi d P y y alcohol-polybasifl to flow from a glass'rod or from a suspended 20 acid resins. thermometer is about 5-6 hours at 225 C., de-

With the above and other objec in V pending on the shape of the reaction kettle. and

' which will be apparent as the description prothe quantity of resin being made. The resultceeds. I have t forth my invention inthe'foling product is a soluble resilient resin having an lowing Specification d ave included t 1- acid number of from 10-20. If the reaction is 25 lowing examples by way of illustration and not interrupted before stringing occurs the product UNITE as a limitation. on cooling is softer and has a somewhat higher Example 1 1 acid number. 18.5 parts by weight of glycerol, 58.2 parts by I Example 3 30 weight of phthalic anhydrideand 23.3 parts by weight of the monobutyl ether of ethylene glycol 7 parts by f g 2 are heated in a suitable container equipped with welght of phthahc anhy 1 e an S y a condenser the temperature of the reaction weight of the w ether of methylene mixture behig gradually raised to C in 4 glycol are heated as in Example 2, except that hours to avoid volatilizing the ether The heatthe reaction kettle need not m 35 .ing. at 225 0. is continued for 1 hour with the i 3 due t bPllmg 0f reflux attached, by which time the esterifieation f d i t i i fi 221 2 has proceeded to a point where very little ether fiexlb e an as an em m will be volatilized oii. The reflux is then reg. Ewample 4 40 mo e heatin at 225 C. is continue unt fih e e snea visco ity is obtained, which is 7- Parts by Welght 55 PM?s preferably h hot resin begins to string I weight of phthal c anhydnde and 27.6 partsby if it is allowed to flow from a suspended therweight I diethyhn are hFated as in Example mometer. The duration of the final heating de- The R5111 thus fumed SOIuble, shghtly less pends on the consistency desired a the size f flexible than the composition of Example 1, and 45 the batch, the reaction mixture losing water and has an 3 number of gradually becoming more viscous as the reac- Example 5 tion proceeds. 12 hours of the last ment1oned heating gives a soluble resilient resin having an Parts y Weight of y L P t y acid number'of 40-50. weight of phthalic anhydride, 25.5 parts by The reaction can also be carried out in a covweight of linseed oil acids and 6.2 parts by weight ered kettle without a reflux condenser by keeping of the monoethyl ether of diethylene glycol are the initial heating temperature down to apheated at 200 C. until the desired viscosity is proximately 180 C. until the esterification has obtained. The time required to attain a conraised the boiling point of the mixture to at leas't sistency such that the reaction mixture begins 55 to string when allowed to flow from a suspended glass rod varies somewhat but 10-12- hours at 200 C. is usually sufficient. The resin formed is very flexible and soluble in aromatic hydrocarbons and in ester solvents and has an acid number of 30-40.

- Example 6 The reaction is carried out as in Example 1 except that 2 to 3 parts by weight of castor oil is added to the reaction mixture. This gives a flexible resin as in Example 1 but the product is less sensitive to temperature change.

Although the above examples are limited to the monobutyl ether of ethylene glycol, the monoethyl ether of diethylene glycol, the monobutyl ether of diethylene glycol, and-.diethylin, other aliphatic hydroxy ethers, such as the monoethyl ether of ethylene glycol, the monomethyl ether of ethylene glycol, monoethylin, and beta-tetrahydrofuryl ethyl methyl carbinol, may be used.

As indicated in Examples 5 and 6, other modifying agents, such as linseed oil acids and castor oil, may enter into the esterification reaction.

The proportions of these modifying hydroxy ethers which I have found to be especially eil'ective are 1 mol. ofhydroxy ether to 1 mol. of glycerol and 2 mols. of phthalic anhydride, although other proportions can be used, depending on the desired consistency of the final resin. Increasing the hydroxy ether content gives softer resins, whereas decreasing this gives harder products. Where other modifying agents, such as drying oil acids, are present, 0.4 mol. of these modifying agents is preferably used in conjunction with 1 mol. of glycerol, 1.4 mols. of phthalic anhydride and 0.2 mol. of hydroxy ether. I

The resins formed in accordance with'my invention are soluble in acetone, ethyl acetate, the monoethyl ether of ethylene glycol, and in mix-- tures of alcohol and toluol. 7

These resins can be used alone in solution or in combination with cellulose esters, such as nitrocellulose, and other ingredients for film-forming purposes, such as wood and metal finishes, for impregnating paper and fabric, or as flexible binders for various materials, such as wood flour or cork. Y

Illustrations of typical compositions containing my new and improved resins are as follows:

Example 7 p a v Pts. by wt. Resin, prepared as in Example 1 9.1 Nitrocellulose (M; sec. viscosity) 18.2 Dibutyl phthalatea 9.1 Castor oil 3.6 Butyl acetate 24.2 Ethyl acetate 12.1 Butyl alcoho 12.1 Ethyl alcohol 6.0 Tolnnl 66.5

The composition as prepared above has a viscosity of A (Gardner-Holdt standard) and contains 23-24% of non-volatile solids.

Example 8 Pts. by wt. Resin, prepared as in Example 5 10.00 Hi-fiash n p 15.00 Cobalt linoleate .03

By the term an esteriflable aliphatic hydro- 582 parts by weight to bring the temperature up to 225 which still contains at least one alcoholic hydroxyl 5 group in order that it may be reactive.

It will therefore be apparent that I have invented a new and useful group of modified polyhydric alcohol-polybasic acid resins which are more flexible and resilient than the polyhydric alcohol-polybasic acid resins heretofore obtain- I able, and that I havedeveloped a new process of making polyhydric alcohol-polybasic acid resins.

As many apparently widely different embodiments of this invention may be made without 15 departing from the spirit and scope thereof, it is to be understood that I-do not limit myself to the specific embodiments thereof except as defined in the appended patent claims.

Iclaim:

1. The process of making a modified polyhydric alcohol-polybasic acid resin which comprises heating a polyhydric aliphatic alcohol, a resinifying polycarboxylic acid, and an esteriflablealiphatic hydrocarbon ether of a polyhydric 25 alcohol.

I, 2. The process of making a modified polyhydric alcohol-polybasic acid resin which comprises heating glycerol, phthalic anhydride, and an esteriflable aliphatic hydrocarbon ether of a 80 polyhydric alcohol.

claim 2, in which the hydroof a polyhydric alcohol in a kettle equipped with '45 a reflux to bring the temperature-up to 225 C. in 4 hours, and thereafter continuing the heating at 225 C. for 1 hour with the reflux attached, re-

and heating until the hot resin if allowed to flow from a suspended thermometer. v 7. The process of claim 6, in which the hydrocarbon-ether of a polyhydric alcohol is a monomethyl ether of ethylene glycol. Y

8. The process of claim 6, in which the hydro 55 carbon ether of a polyhydric alcohol is a monoethyl ether of ethylene glycol.

9. The process of claim 6, in which the hydrocarbon ether of a polyhydric alcohol is the monobutyl ether of ethylene glycol. 60

10. The process of making a modified po y ydric alcohol-polybasic acid resin which comprises gradually heating 18.5 parts by weight of glycerol, of phthalic anhydride and 23.3 parts by weight of the monobutyl ether of 65 ethylene glycol in a kettle equipped with a reflux C. in 4 hours, and thereafter continuing the heating at 225' C. for 1 hour. with the reflux attached, removing the reflux and heating until the hot resin begins to 70 string if allowed to flow from a suspended thergradually heating 18.5 parts by weight ofglycerol,

58.2 parts by weight of phthalic anhydride and 23.3 parts by weight 01! the monobutyl ether of ethylene glycol in a kettle equipped with a reflux to bring the temperature up to 225 C. in 4 hours, and thereafter continuing the heating at 225 C. for 1 hour with the reflux attached, removing the reflux and heating at 225 C. for 12 hours. f

12. A modified polyhydric alcohol-polybasic acid resin comprising the reaction product of a 15. The resin 01! claim 13, m which the hydrocarbon ether of a polyhydric alcohol is a monoethyl ether of ethylene glycol.

16. The resin of claim 13, in which the hydrocarbon ether of a poiyhydric alcohol is the monobutyl ether of ethylene glycol.

17. A coating composition comprising the reaction product of glycerol, phthalic anhydride, 4

and an esterifiable aliphatic hydrocarbon ether of a polyhydric alcohol.

18. The composition of claim 1'7, in which the hydrocarbon ether of a polyhydric alcohol is a monomethyl ether of ethylene glycol.

19. The composition of claim 17, in which the hydrocarbon ether of a polyhydric alcohol is a, 15

monoethyl ether of ethylene glycol.

20, The composition of claim 1'7, in which the hydrocarbon ether of a polyhydric alcohol is the monobutyl ether of ethylene glycol.

7 BEN E. sonmrson. 

